CN107759641A - α diimine nickel complexes, preparation method and application - Google Patents
α diimine nickel complexes, preparation method and application Download PDFInfo
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- CN107759641A CN107759641A CN201711134441.0A CN201711134441A CN107759641A CN 107759641 A CN107759641 A CN 107759641A CN 201711134441 A CN201711134441 A CN 201711134441A CN 107759641 A CN107759641 A CN 107759641A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
Abstract
α diimine nickel complexes, preparation method and application, it is related to the preparing technical field of high aromatic hydrocarbons, such catalyst is with AlEt2Cl is that co-catalyst forms catalyst system, and the trace amounts of olefin in reformed oil is removed by the trace amounts of olefin polymerisation in catalytic reforming generation oil under conditions of non-hydrogen, the deolefination process warm and, reaction temperature is low（Room temperature ~ 70 DEG C）, the reaction time is short（5min~15min）, catalyst amount is low（Ppm levels）, olefinic polymerization formed certain molecular weight olefin polymerization there is no harmful effect to the following process of reformed oil.
Description
Technical field
The present invention relates to the preparing technical field of high aromatic hydrocarbons.
Background technology
Reformed oil（The intermediate products of aromatics production）In contain a certain amount of olefin impurity, these olefin impurity properties
It is very active, it is easy to which that polymerization, which forms colloid, influences the quality of aromatic hydrocarbon product, even if olefin(e) centent is considerably less（Only ppm levels）
Very detrimental effect can be produced to subsequent reactions process.In order to obtain qualified industrial chemicals and ensure the smooth of subsequent technique
Carry out, it is necessary to by a small amount of olefin removal in reformed oil, to improve the economic benefit of aromatic hydrocarbons processing technology.
Reforming and generating oil-off olefin technique has following 4 kinds at present：It is clay-filtered；Hydrogenation catalyst refines；Molecular sieve
Catalytic refining and 4. combination are refined.
Wherein methodWithIt is maturation process, is industrially applied, it is clay-filtered mainly to pass through alkene
To adsorb on carclazyte or polymerize on a small quantity to remove trace amounts of olefin, hydrofinishing is the hydrogen catalyzed and olefine reaction in hydro condition,
Make alkene saturation, so as to remove alkene, it is catalytic action by molecular sieve that molecular sieve catalytic is refined, make alkene with generation oil
Aromatic hydrocarbons be alkylated reaction, to remove trace amounts of olefin therein, currently develop focus, combination process for refining is in test.
He Yaxian etc.（Development [J] the Speciality Petrochemicals progress of refined aromatic hydrocarbons granular carclazyte, 2001,2 (6)：15-
22）Using X x ray diffractions, pore-size distribution test and deolefination evaluation test, high-quality carclazyte mineral resources is determined, have studied acidifying
The influence of condition, binding agent and sintering temperature to granular carclazyte performance, is prepared for high-quality granular carclazyte.
Wang Ming etc.（Industrial Evaluation of Particulate Clay for Aromatic Refining [J] fine-chemical intermediates, 2004,34 (4)：66-
72.）：By industrial side line evaluation test, under the conditions of device technique, to 4 kinds of Emathlites in oil-off olefin processing is reformed
Effect evaluated, and make technical economic analysis.
It is clay-filtered to exist except alkene temperature is higher, it is necessary to 180~210 DEG C, short life, only 2~3 months, Yi Jigu
Technical problem more than giving up.
The content of the invention
For technical problem existing for existing modified argil catalytic eliminating alkene, the present invention provides a kind of alpha-diimine nickel and matched somebody with somebody
Compound.
The structural formula of alpha-nickel diimine compound of the present invention is：
Wherein, R1For independent hydrogen, methyl and isopropyl.
Catalyst of the above alpha-nickel diimine compound as substituted diphenylamine methyl, can catalysis in olefine polymerization, have compared with
High stability.
Second purpose of the invention is to propose the preparation method of above complex.
Comprise the following steps：
1）Under the catalysis of p-methyl benzenesulfonic acid, in aromatic solvent, by diacetyl and 2,6- benzhydryl -4- methylanilines mix
Close and carry out back flow reaction, obtain compound（Ⅱ）：3-（2,6- benzhydryl -4- methylphenyliminos）- 2- butanone；
Wherein aromatic solvent in benzene, toluene or dimethylbenzene at least any one.
Reaction equation is as follows：
(Ⅱ)
2）Under the catalysis of p-methyl benzenesulfonic acid, in aromatic solvent, by 3-（2,6- benzhydryl -4- aminomethyl phenyl imido
Base）- 2- butanone mixes with aminated compounds carries out back flow reaction, obtains compound（Ⅲ）：The asymmetric α of benzhydryl substitution-
Diimide ligand；
Wherein aromatic solvent in benzene, toluene or dimethylbenzene at least any one.
Reaction equation is as follows：
3）In dichloromethane, by compound（Ⅲ）（The asymmetric alpha-diimine part of benzhydryl substitution）With (DME) NiBr2
（DME=1,2- dimethoxy-ethanes）Reaction, generate alpha-diimine complex.
Reaction equation is as follows：
Above-mentioned building-up process, reaction condition is gentleer, and yield is higher.
Further, step 1 of the present invention）In, 2, the 6- benzhydryls -4- methylanilines and p-methyl benzenesulfonic acid
The phasor ratio that feeds intake for 1: 0.1, the rate of charge of diacetyl and 2,6- the benzhydryl -4- methylanilines is 1: 1.Wherein to first
Benzene sulfonic acid is catalyst, further increases the amount of p-methyl benzenesulfonic acid, will not further improve reaction rate, that is, reduces reaction and use
When；The rate of charge of diacetyl and 2,6- benzhydryl -4- methylanilines is 1: 1, it is ensured that the almost reaction completely of raw material, can
To increase one of which material（Inexpensively）Dosage, ensure that another material reaction finishes.
The step 1）Reaction temperature is carried out under the conditions of 60~90 DEG C, and reaction takes solid phase true after being washed with methanol after terminating
Sky is dried, and obtains 3-（2,6- benzhydryl -4- methylphenyliminos）- 2- butanone.If reaction temperature is less than 60 DEG C, reaction
Speed is too slow, hardly reacts in other words, little to improving reaction rate use during more than 90 DEG C.
The step 2）In, the aminated compounds is aniline, 2,6- dimethylanilines or 2,6-DIPA.Adopt
With the specific amine, the part thus formed, deolefination effect is good.
The step 2）In, the molar ratio of formula (II) compound and amine, p-methyl benzenesulfonic acid is 1: 1: 0.1.
P-methyl benzenesulfonic acid is catalyst, further increases the amount of p-methyl benzenesulfonic acid, will not further improve reaction rate, that is, reduces reaction
Used time；The rate of charge of diacetyl and 2,6- benzhydryl -4- methylanilines is 1: 1, it is ensured that the almost reaction completely of raw material,
One of which material can be increased（Inexpensively）Dosage, ensure that another material reaction finishes.
The step 2）In, the reaction is carried out at 70~90 DEG C, and reaction takes solid phase true after being washed with methanol after terminating
Sky is dried, and obtains the asymmetric alpha-diimine part of benzhydryl substitution.If during less than 70 DEG C, reaction rate is too slow, more than 90
DEG C when, to improve reaction rate use it is little.
Above-mentioned steps 3）In, the compound (III) and (DME) NiBr2Molar ratio be 1: 1.Present invention use etc.
Molar reactive can guarantee that reaction is more complete.
The step 3）In, the reaction time is 12~24 hours.Under the conditions of this reaction time, it can guarantee that and reach required
Conversion ratio, further improve the reaction time, but raising conversion ratio use is little, less than 12h, is also finished without reaction.
3rd purpose of the invention is to propose the application of above alpha-nickel diimine compound.
By alpha-nickel diimine compound and AlEt2Cl, toluene are dissolved in CH2Cl2In catalyst system is made, by catalyst
System mixes with reformed oil is reacted, and obtains the reformed oil of removing alkene.
The late transition metal catalyst that the present invention is coordinated using nickel as metal center, using a kind of asymmetric neighbour
The alpha-diimine structure of the big steric hindrance in position, installs different substituents to improve at the ortho position of big steric hindrance aniline moiety opposite side aniline
Catalyst performance.Wherein Ni-iPr catalyst is in catalyzing aromatic hydrocarbon（Reformed oil）In trace amounts of olefin polymerization, show high
Catalytic activity, react and carried out under conditions of as mild as a dove, the reaction time is short, generate oil trace amounts of olefin polymerization after product
For the hydrocarbon polymer of HMW, when reformed oil following process is handled, without harmful effect.
Embodiment
Following embodiments have been illustrated the present invention particular content, give part and metal complex synthesis,
The method of reforming and generating oil-off olefin.Wherein the synthesis of complex and catalyst preparation are carried out under anhydrous and oxygen-free, reform life
Into oil-off olefin course of reaction carried out in the case where completely cutting off air conditionses.
First, the synthesis technique of complex：
Embodiment 1：
2 moles of diacetyl, 1 mole of 2,6- benzhydryl -4- methylanilines and 0.1 mole of p-methyl benzenesulfonic acid are taken,
Heated after being dissolved in toluene at 80 DEG C, stir 24h, be then refluxed for point water 3-14 days, the extent of reaction is during which monitored by a plate.
After the completion of reaction, toluene is spin-dried for there is a small amount of yellow solid to separate out, methanol is added afterwards, filters, gained yellow solid uses first
Alcohol is washed 3 times, and formula (II) compound is obtained after vacuum drying：3-（2,6- benzhydryl -4- methylphenyliminos）- 2- butanone.
By the p-methyl benzenesulfonic acid of the equivalent of obtained formula (II) compound 1, the equivalent of aniline 1 and 0.1 equivalent, toluene is dissolved in
Heated afterwards at 80 DEG C, stir 24h.It is then refluxed for point water 3-14 days, the extent of reaction is during which monitored by a plate.Reaction is completed
Afterwards, toluene is spin-dried for there is a small amount of yellow solid to separate out, and is added methanol afterwards, is filtered, gained yellow solid uses methanol washing 3
Secondary, vacuum drying obtains 2- (2,6- benzhydryl -4- methylphenyliminos) -3- phenylimino butane（Formula (III) chemical combination
Thing（1））, yield 91%.
2- (2,6- benzhydryl -4- methylphenyliminos) -3- phenylimino butane（Formula (III) compound（1））'s
Structural formula is as follows：
In dichloromethane, by 2- (2,6- benzhydryl -4- methylphenyliminos) -3- phenyliminos butane and (DME)
NiBr2（DME=1,2- dimethoxy-ethanes）Reaction, generate alpha-diimine complex.
Embodiment 2：
Take excessive 2 moles of diacetyl, 1 mole of 2,6- benzhydryl -4- methylanilines and 0.1 mole to methylbenzene sulphur
Acid, heated after being dissolved in dimethylbenzene at 80 DEG C, stir 24h, be then refluxed for point water 3-14 days, reaction is during which monitored by a plate
Degree.After the completion of reaction, it is spin-dried for mixing hexichol to there is a small amount of yellow solid to separate out, adds methanol afterwards, filter, gained yellow is consolidated
Body is washed 3 times using methanol, and formula (II) compound is obtained after vacuum drying：3-（2,6- benzhydryl -4- aminomethyl phenyl imido
Base）- 2- butanone.
By the equivalent of obtained formula (II) compound 1, the equivalent of 2,6- dimethylaniline 1 and 0.1 equivalent to methylbenzene sulphur
Acid, heated after being dissolved in dimethylbenzene at 80 DEG C, stir 24h.It is then refluxed for point water 3-14 days, reaction is during which monitored by a plate
Degree.
After the completion of reaction, mixed xylenes is spin-dried for there is a small amount of yellow solid to separate out, methanol is added afterwards, filters, gained
Yellow solid is washed 3 times using methanol, and vacuum drying obtains 2- (2,6- benzhydryl -4- methylphenyliminos) -3- (2,6-
3,5-dimethylphenyl imino group) butane（Formula (III) compound（2））, yield 93%.
2- (2,6- benzhydryl -4- methylphenyliminos) -3- (2,6- 3,5-dimethylphenyls imino group) butane（Formula (III)
Compound（2））Structural formula it is as follows：
Embodiment 3：
Take excessive 2 moles of diacetyl, 1 mole of 2,6- benzhydryl -4- methylanilines and 0.1 mole to methylbenzene sulphur
Acid, heated after being dissolved in benzene at 80 DEG C, stir 24h, be then refluxed for point water 3-14 days, reaction interval is during which monitored by a plate
Degree.After the completion of reaction, benzene is spin-dried for there is a small amount of yellow solid to separate out, methanol is added afterwards, filters, gained yellow solid uses first
Alcohol is washed 3 times, and formula (II) compound described in claim 1 is obtained after vacuum drying：3-（2,6- benzhydryl -4- methylbenzenes
Base imino group）- 2- butanone.
By the equivalent of obtained formula (II) compound 1, the equivalent of 2,6-DIPA 1 and 0.1 equivalent to methylbenzene
Sulfonic acid, heated after being dissolved in benzene at 80 DEG C, stir 24h.It is then refluxed for point water 3-14 days, reaction interval is during which monitored by a plate
Degree.After the completion of reaction, benzene is spin-dried for there is a small amount of yellow solid to separate out, methanol is added afterwards, filters, gained yellow solid uses first
Alcohol washs 3 times, and vacuum drying obtains 2- (2,6- benzhydryl -4- methylphenyliminos) -3-, and (2,6- diisopropyl phenyls are sub-
Amino) butane（Formula（Ⅲ）Compound（3））, yield 96%.
2- (2,6- benzhydryl -4- methylphenyliminos) -3- (2,6- diisopropylphenylimidos) butane（Formula
（Ⅲ）Compound（3））Structural formula it is as follows：
Embodiment 4：(2,6- benzhydryl -4- methylphenyliminos) -3- phenylimino butane nickel complexes (Ni-H)
Synthesis：
Formula (III) compound 2- (2,6- benzhydryl -4- methylphenyliminos) -3- phenyliminos prepared by Example 1
Butane 5.8g (10mmol) and (DME) NiBr23.1g（10mmol）Add in Schlenk flasks.In N2Note is used under atmosphere
Emitter adds CH2Cl2（200mL）, mixture is stirred at room temperature 12 hours.Filtering gained suspension, is removed in vacuum solvent.
Gained powder ether（2×100mL）Washing, is then dried in vacuo, obtains brown solid powder, i.e. complex formula at room temperature
(Ⅰ)：Catalyst n i-H, yield 78%.
The structural formula of complex formula (I) is as follows：
Embodiment 5：2- (2,6- benzhydryl -4- methylphenyliminos) -3- (2,6- 3,5-dimethylphenyls imino group) butane nickel
The synthesis of complex (Ni-Me)：
Step has put into formula (III) compound 2- (2, the 6- benzhydryl -4- aminomethyl phenyls Asias of the preparation of embodiment 2 with embodiment 4
Amino) -3- (2,6- 3,5-dimethylphenyl imino group) butane (6.1g, 10mmol), obtain brown solid powder, i.e. catalyst n i-
Me, yield 80%.
Catalyst n i-Me（2- (2,6- benzhydryl -4- methylphenyliminos) -3- (2,6- 3,5-dimethylphenyl imido
Base) butane nickel complex）Structural formula it is as follows：
Embodiment 6：2- (2,6- benzhydryl -4- methylphenyliminos) -3- (2,6- diisopropylphenylimidos) butane
Nickel complex (Ni-iPr synthesis)：
Step has put into formula (III) compound 2- (2, the 6- benzhydryl -4- aminomethyl phenyls Asias of the preparation of embodiment 3 with embodiment 4
Amino) -3- (2,6- diisopropylphenylimido) butane (6.7g, 10mmol), obtain brown solid powder, i.e. catalyst
Ni-iPr, yield 81%.
Catalyst n i-iPr（(2,6- diisopropyl phenyls are sub- by 2- (2,6- benzhydryl -4- methylphenyliminos) -3-
Amino) butane nickel complex）Structural formula it is as follows：
2nd, catalytic reforming generation oil-off olefin polymerisation application：
Catalyst system is prepared：Under conditions of air is completely cut off, added in the following proportions into pressure-resistant glass container
2mLAlEt2Cl, 200 mL toluene, it is dissolved in 20mLCH2Cl2Embodiment 4-6 made from the 24 μm of ol stirrings of each nickel complex.
By the catalyst system prepared and reformed oil（Raw material bromine index is 2372mgBr/100g oil）Necessarily to compare
Example is injected into reactor（Completely cut off air, holding pressure is pressure-fired）Stirring, modulation reaction temperature, reaction time etc., sampling
The bromine index of analytical reactions product.
Reaction result is shown in Table 1（Embodiment 4 is corresponded to using catalyst n i-H, Ni-Me corresponds to embodiment 5, Ni-iPr is corresponding real
Apply example 6）.
The reforming and generating oil-off olefin effect table of table 1.
In upper table, catalyst amount refers to prepared catalyst system total amount（Including solvent etc.）/ reformed oil amount（w）.
As seen from the above table：The deolefination that catalyst of the present invention is used for reformed oil reacts, and olefin removal rate is high, reacts bar
Part is gentle, and the reformed oil bromine index after processing is below 100 mgBr/100g oil（Industry standards call is less than 100
MgBr/100g oil）, especially Ni-iPr catalyst system and catalyzing effects are more preferable.
Claims (10)
1. alpha-nickel diimine compound, its structural formula are：
Wherein, R1For independent hydrogen, methyl and isopropyl.
2. the preparation method of alpha-nickel diimine compound as claimed in claim 1, it is characterised in that comprise the following steps as follows：
1）Under the catalysis of p-methyl benzenesulfonic acid, in aromatic solvent, by diacetyl and 2,6- benzhydryl -4- methylanilines mix
Close and carry out back flow reaction, obtain compound 3-（2,6- benzhydryl -4- methylphenyliminos）- 2- butanone；The aromatic solvent
In benzene, toluene or dimethylbenzene at least any one；
2）Under the catalysis of p-methyl benzenesulfonic acid, in aromatic solvent, by 3-（2,6- benzhydryl -4- aminomethyl phenyl imido
Base）- 2- butanone mixes with aminated compounds carries out back flow reaction, and the asymmetric alpha-diimine for obtaining the substitution of compound benzhydryl is matched somebody with somebody
Body；The aromatic solvent in benzene, toluene or dimethylbenzene at least any one；
3）In dichloromethane, by the asymmetric alpha-diimine part that benzhydryl substitutes and (DME) NiBr2Reaction, generation α-
Diimine nickel complex.
3. the preparation method of alpha-nickel diimine compound according to claim 1, it is characterised in that the step 1）In, it is described
The molar ratio of 2,6- benzhydryl -4- methylanilines and p-methyl benzenesulfonic acid is 1: 0.1, diacetyl and 2, the 6- hexichol
The rate of charge of methyl -4- methylanilines is 1: 1.
4. the preparation method of alpha-nickel diimine compound according to Claims 2 or 3, it is characterised in that the step 1）Reaction
Temperature is carried out under the conditions of 60~90 DEG C, and reaction takes solid phase to be dried in vacuo after being washed with methanol after terminating, and obtains 3-（2,6- hexichol
Methyl -4- methylphenyliminos）- 2- butanone.
5. the preparation method of alpha-nickel diimine compound according to claim 2, it is characterised in that the step 2）In, it is described
Aminated compounds is aniline, 2,6- dimethylanilines or 2,6- diisopropyl anilines.
6. according to the preparation method of the alpha-nickel diimine compound of claim 2 or 5, it is characterised in that the step 2）In,
The 3-（2,6- benzhydryl -4- methylphenyliminos）The molar ratio of -2- butanone and aniline, p-methyl benzenesulfonic acid is
1∶1∶0.1。
7. according to the preparation method of the alpha-nickel diimine compound of claim 2 or 5, it is characterised in that the step 2）In,
The reaction temperature is carried out at 70~90 DEG C, and reaction takes solid phase to be dried in vacuo after being washed with methanol after terminating, and obtains hexichol first
The asymmetric alpha-diimine part of base substitution.
8. the preparation method of alpha-nickel diimine compound according to claim 2, it is characterised in that the step 3）In, it is described
The asymmetric alpha-diimine part and (DME) NiBr of benzhydryl substitution2Molar ratio be 1: 1.
9. according to the preparation method of the alpha-nickel diimine compound of claim 2 or 8, it is characterised in that the step 3）In,
Reaction time is 12~24 hours.
10. the application of complex as claimed in claim 1, by alpha-nickel diimine compound and AlEt2Cl, toluene are dissolved in
CH2Cl2In catalyst system is made, catalyst system is mixed with reformed oil and reacted, obtain removing alkene reformation
Generation oil.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109942638A (en) * | 2019-04-19 | 2019-06-28 | 常州大学 | Asymmetric alpha-diimine nickel (II) complex that methylbenzyl is replaced containing ortho position two for vinyl polymerization |
| CN110590980A (en) * | 2019-10-09 | 2019-12-20 | 中国科学院长春应用化学研究所 | Asymmetric alpha-diimine nickel catalyst and preparation method and application thereof |
| CN112175018A (en) * | 2020-10-10 | 2021-01-05 | 山西大学 | Diphenyl methoxyl group-containing pyridine imine cobalt complex and preparation method and application thereof |
| CN112745359A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Diimine metal complex and preparation method and application thereof |
| CN112745363A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Amino imine metal complex and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104250270A (en) * | 2013-06-28 | 2014-12-31 | 中国石油天然气股份有限公司 | Asymmetric benzhydryl alpha-diimine nickel complex, preparation and application thereof |
| CN107641138A (en) * | 2017-09-27 | 2018-01-30 | 常州大学 | For ethene and the asymmetric α diimine nickels containing the substitution of ortho position benzhydryl of 1 hexene oligomerization（Ⅱ）Complex |
-
2017
- 2017-11-16 CN CN201711134441.0A patent/CN107759641A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104250270A (en) * | 2013-06-28 | 2014-12-31 | 中国石油天然气股份有限公司 | Asymmetric benzhydryl alpha-diimine nickel complex, preparation and application thereof |
| CN107641138A (en) * | 2017-09-27 | 2018-01-30 | 常州大学 | For ethene and the asymmetric α diimine nickels containing the substitution of ortho position benzhydryl of 1 hexene oligomerization（Ⅱ）Complex |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109942638A (en) * | 2019-04-19 | 2019-06-28 | 常州大学 | Asymmetric alpha-diimine nickel (II) complex that methylbenzyl is replaced containing ortho position two for vinyl polymerization |
| CN110590980A (en) * | 2019-10-09 | 2019-12-20 | 中国科学院长春应用化学研究所 | Asymmetric alpha-diimine nickel catalyst and preparation method and application thereof |
| CN112745359A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Diimine metal complex and preparation method and application thereof |
| CN112745363A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Amino imine metal complex and preparation method and application thereof |
| CN112745359B (en) * | 2019-10-31 | 2022-10-21 | 中国石油化工股份有限公司 | Diimine metal complex and preparation method and application thereof |
| CN112745363B (en) * | 2019-10-31 | 2022-10-21 | 中国石油化工股份有限公司 | Amino imine metal complex, preparation method and application thereof |
| CN112175018A (en) * | 2020-10-10 | 2021-01-05 | 山西大学 | Diphenyl methoxyl group-containing pyridine imine cobalt complex and preparation method and application thereof |
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